期刊
INORGANICS
卷 11, 期 9, 页码 -出版社
MDPI
DOI: 10.3390/inorganics11090372
关键词
phosphinocarboxamide; metallacycle; ruthenium; P ligands; coordination chemistry
This study reports the synthesis of ruthenium complexes with phosphinocarboxamide ligands and their use in forming metallacycles through halide abstraction/deprotonation reactions. The coordination and structure of these complexes were studied using X-ray diffraction and NMR spectroscopy, revealing the presence of intramolecular hydrogen bonding and rotational isomers in solution.
Ruthenium complexes of phosphinocarboxamide ligands, and their use to form metallacycles using halide abstraction/deprotonation reactions are reported. Thus, [Ru(p-cym){PPh2C(=O)NHR}Cl2; R = iPr (1), Ph (2), p-tol (3)] and [Ru(p-cym){PPh2C(=O)N(R)C(=O)N(H)R}Cl2; R = Ph (4), p-tol (5)] were synthesized from [(p-cym)RuCl2]2 (p-cym = para-cymene) and phosphinocarboxamides or phosphinodicarboxamides, respectively. Single-crystal X-ray diffraction measurements on 1-5 reveal coordination to ruthenium through the phosphorus donor, with an intramolecular hydrogen bond between the amine-bound proton and a metal-bound chloride. Six-membered metallacycles formed by halide abstraction/deprotonation of complexes 4 and 5 afforded [Ru(p-cym){& kappa;2-P,N-PPh2C(=O)N(R)C(=O)NR}Cl] [R = Ph (6), p-tol (7)]. These species exist as a mixture of two rotational isomers in solution, as demonstrated by NMR spectroscopy.
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